Method for manufacturing all-solid-state thin-film batteries

Abstract

A process for fabrication of all-solid-state thin film batteries, may include batteries including a film of anode materials, a film of solid electrolyte materials and a film of cathode materials. Each of these three films may be deposited using an electrophoresis process. The anode film and the cathode film may each be deposited on a conducting substrate, preferably a thin metal sheet or band, or a metalized insulating sheet or band or film. The conducting substrates or their conducting elements may be useable as battery current collectors, the electrolyte film may be deposited on the anode and/or cathode film. The process may also include stacking the sheets or bands so as to form at least one battery with a “collector/anode/electrolyte/cathode/collector” type of stacked structure.

The invention claimed is: 
     
       1. A process for fabrication of an all-solid-state thin film battery, the process comprising:
 depositing, using an electrophoresis process without any binders, an anode film comprising an anode active material on a first current collector and a cathode film comprising a cathode active material on a second current collector; 
 depositing, using an electrophoresis process without any binders, an electrolyte film comprising an electrolyte material on at least one of the anode film and the cathode film; 
 stacking the anode film formed on the first current collector and the cathode film formed on the second current collector to form a stacked structure having a collector/anode/electrolyte/cathode/collector stacked structure to obtain an all-solid-state thin film battery; and 
 consolidating, to a porosity of less than 15%, at least one of the anode film, the cathode film, and the electrolyte film to increase the density of the at least one of the anode film, the cathode film, and the electrolyte film, by mechanical consolidation using one or more of isostatic pressing or hot pressing, 
 wherein:
 the anode active material, the cathode active material, and the electrolyte material comprise nanoparticles having an average size of less than 100 nm, 
 the respective thicknesses of the deposited anode film, the deposited cathode film, and the deposited electrolyte film are less than 5 μm, and 
 the consolidating of the at least one of the anode film, the cathode film, and the electrolyte film is further performed under a vacuum or an inert atmosphere. 
 
 
     
     
       2. The process of  claim 1 , further comprising, after the stacking, consolidating to a porosity of less than 10% at least one of the anode film, the cathode film, and the electrolyte film to increase the density of the at least one of the anode film, the cathode film, and the electrolyte film mechanically consolidation using one or more of isostatic pressing or hot pressing, wherein the consolidation is further performed under a vacuum or an inert atmosphere. 
     
     
       3. The process of  claim 1 , further comprising, after the stacking, consolidating to a porosity of less than 5% at least one of the anode film, the cathode film, and the electrolyte film to increase the density of the at least one of the anode film, the cathode film, and the electrolyte film by mechanical consolidation using one or more of isostatic pressing or hot pressing, wherein the consolidation is further performed under a vacuum or an inert atmosphere. 
     
     
       4. The process of  claim 1 , wherein the consolidation further includes a thermal consolidation to be performed before the mechanical consolidation. 
     
     
       5. The process of  claim 1 , wherein the consolidation further includes a thermal consolidation to be performed after the mechanical consolidation. 
     
     
       6. The process of  claim 1 , wherein the first current collector and the second current collector are composed of aluminum. 
     
     
       7. The process of  claim 6 , wherein the aluminum comprises electro-polished aluminum foil. 
     
     
       8. The process of  claim 7 , wherein the first current collector and the second current collector have a thickness of 1 to 10 μm. 
     
     
       9. The process of  claim 1 , wherein at least one of the anode active material, the cathode active material and the electrolyte material comprises nanoparticles having an average size of less than 50 nm. 
     
     
       10. The process of  claim 1 , wherein the anode active material comprises at least one of:
 tin oxinitrides (SnO x N y ); 
 mixed silicon and tin oxinitrides (Si a Sn b O y N z  where a>0, b>0, a+b≤2,0<y≤4.0<z≤3) (also called SiTON), and SiSn 0.87 O 1.2 N 1.72 ; and oxinitrides in the form Si a Sn b C c O y N z  where a>0, b>0, a+b≤2, 0<c−10, 0<y<24, 0<z<17; Si a Sn b C c O y N z X n  and Si a Sn b O y N z X n  where X n  is at least one of the elements F, Cl, Br, I, S, Se, Te, P, As, Sb, 
 Bi, Ge, and Pb; 
 Si x N y  type nitrides, Sn x N y , Zn x N y , Li 3−x M x N (where M=Co, Ni, Cu); and 
 SnO 2 , Li 4 Ti 5 O 12 , SnB 0.6 P 0.4 O 2.9  oxides. 
 
     
     
       11. The process of  claim 1 , wherein the anode active material is chosen from Si x N y  type nitrides (in which x=3 and y=4), Sn x N y  type nitrides (in which x=3 and y=4), Zn x N y  type nitrides (in which x=3 and y=4), and Li 3−x M x N type nitrides (where M+Co, Ni, Cu). 
     
     
       12. The process of  claim 1 , wherein the anode active material comprises SiSn 0.87 O 1.2 N 1.72 . 
     
     
       13. The process of  claim 1 , wherein the cathode active material comprises at least one of:
 LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiMn 1.5 Ni 0.5 O 4 , LiMn 1.5 Ni 0.5−x M x O 4  oxides (where M is selected from among Al, Fe, Cr, Co, Rh, Nd, other rare earths and in which 0<x<0.1), LiFeO 2 , LiMn 1/3 Ni 1/3 Ni 1/3 Co 1/3 O 4 ; 
 LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 , Li 3 V 2 (PO 4 ) 3  phosphates; and 
 all lithiated forms of the following chalcogenides: V 2 O 5 , V 3 O 8 , TiS 2 , TiO y S z , WO y S z , CuS, and CuS 2.    
 
     
     
       14. The process of  claim 1 , wherein the electrolyte material comprises at least one of:
 lithium compounds based on lithium oxintride and phosphorus (LiPON) in the form Li x PO y N z  where xϵ2.8 and  2 y=3z ϵ7.8 and 0.16 ≤z ≤0.4, variants in the form Li w PO x N y S z  where  2 x+ 3 y+ 2 z=5=w and 3.2≤x≤x≤3.8, 0.13≤y≤0.4, 0≤z≤0.2, 2.9≤w≤3.3, and in the form Li t P x Al y O u N v S w  where 5x+3y=5, 2u+3v+ 2 w=5+t, 2, 9≤t≤3, 3, 0.94≤x≤0.84, 0.094≤y≤0.26, 3.2≤u≤3.8, 0.13≤v≤0.46, 0≤w≤0.2; 
 lithium compounds based on lithium oxinitride, phosphorus and silicon (LiSiPON); 
 lithium oxinitrides of the LiBON, LiBSO, LiSiPON, LiSON, thio-LiSiCON, LiPONB types (where B, P and S represent boron, phosphorus and sulfur respectively); 
 compounds La 0.51 Li 0.34 Ti 2.94 , Li 3.4 V 0.4 Ge 0.6 O 4 , Li 2 O 4 , Li 2 O-Nb 2 O s , LiAlGaSPO 4 ; and 
 formulations based on Li 4 SiO 4 , Li 3 PO 4 , Li 2 CO 3 , B 2 O 3 , Li 2 O, Al(PO 3 ) 3LiF, P 2 S 3 , Li 2 S, Li 3 N, Li 14 Z n (GeO 4 ) 4  , Li 3.6 Ge 0.6 V 0.4 O 4 , LiTi 2 (PO 4 ) 3 , Li 0.35 La 0.55 TiO 3 , Li 3.25 Ge 0.25 P 0.25 S 4 , Li 1.3 Al 0.3 Ti 1.7 (PO 4)   3 , Li 1+x Al x M 2−x (PO 4 ) 3  (where M=Ge, Ti, and/or Hf, and where  0 <x< 1 ), Li 1+x+y Al x Ti 2−x Si y P 3−y O 12  (where 0≤x≤1 and 0≤y≤1), and Li 1+x+z M x (Ge 1−y Ti y ) 2−x Si z P 3−z O 12  (where 0 x≤0.8;  0 ≤y≤1.0; 0≤z≤0.6). 
 
     
     
       15. The process of  claim 1 , wherein the electrolyte material comprises Li 2.9 PO 3.3 N 0.45.    
     
     
       16. The process of  claim 1 , wherein the electrolyte material comprises Li 1.9 Si 0.28 P 1.0 O 1.1 N 1.0.    
     
     
       17. The process of  claim 1 , wherein the electrolyte material is chosen from formulations based on 4.9Lil-34, 1Li 2 O-61B 2 O 3 , 0.30Li 2 S-0.26B 2 S 3 -0.44Lil, 60Li 2 S-40SiS 2 , 0.02Li 3 PO 4 -0.98(Li 2 S-SiS 2 ), 2(Li 1.4 Ti 2 Si 0.4 P 2.6 O 12 )-AlPO 4 , and 0.7Li 2 S-0.3P 2 S 5.    
     
     
       18. The process of  claim 17 , wherein electron conducting and/or lithium ion conducting nanoparticles are deposited at the same time as the electrode material nanoparticles. 
     
     
       19. The process of  claim 18 , wherein the conducting nanoparticles are composed of one of ceramic or vitroceramic materials chosen from among LIPON type compounds, LISIPON type compounds, Li 4 SiO 4 , Li 3 PO 4 , Li 2 CO 3 , B 2 O 3 , Li 2 O, Al(PO 3 ) 3 LiF, P 2 S 3 , Li 2 S, Li 3 N, Li 14 Zn(GeO 4 ) 4 , Li 3.6 Ge 0.6 V 0.4 O 4 , LiTi 2 (PO 4 ) 3 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 0.35 La 0.55 TiO 3 , Li 3.25 Ge 0.25 P 0.25 S 4 , Li 1+x Al x M 2−x (PO 4 ) 3 , with M=Ge, Ti, Hf and 0<x<1, Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 , Li 1+x+z M x (Ge 1−y Ti y ) 2−x Si z P 3−z O 12 , (0=<=<0,8;  0 =<y=<1,0; 0=<z=<0,6) powder mixtures 4,9Lil-34,1Li 2 O-61B 2 O 3 , 30Li 2 O-61B 2 O 3 , 30Li 2 S-26B 2 S 3 -44Lil, 60Li 2 S-40SiS 2 , 2Li 3 , PO 4 -98(Li 2 S-SiS 2 ), (Li 1.4 Ti 2 Si 0.4 P 2.6 O 12 )/ AIPO 4 (in ratio 2:1), 70Li 2 S-30P 2 S 5 , LiBO 2 , LiBON, LiBSO, LiSiPON, LiSON, thio-LiSiCON, La 0.51 Li 0.34 TiO 2.94 , Li 3.4 V 0.4 Ge 0.6 O4, Li 2 O-Nb 2 O 5 , LiPONB, and LiAlGaSPO 4.    
     
     
       20. The process of  claim 18 , wherein the conducting nanoparticles are Li 2.9 PO 3.3 N 0.46.    
     
     
       21. The process of  claim 18 , wherein the conducting nanoparticles are Li 1.9 Si 0.2 P 1.0 O 1.1 N 1.0.    
     
     
       22. The process of  claim 1 , wherein at least one of the anode active material, the cathode active material, and the electrolyte material comprises nanoparticles having an average size of less than 30 nm. 
     
     
       23. A process for fabrication of an all-solid-state thin film battery, the process comprising:
 depositing, using an electrophoresis process without any binders, a film of anode active material comprising nanoparticles having an average size of less than 100 nm on a first current collector, and a film of cathode active material comprising nanoparticles having an average size of less than 100 nm, on a second current collector; 
 depositing on at least one of the film of anode materials and the film of cathode materials using an electrophoresis process without any binders, a film of solid electrolyte material comprising nanoparticles having an average size of less than 100 nm; 
 stacking the film of anode materials formed on the current collector and the film of cathode materials formed on the current collector to form a stacked structure having a collector/anode/electrolyte/cathode/collector stacked structure to obtain an all-solid-state thin film battery; and 
 consolidating, to a porosity of less than 15%, at least one of the film of anode materials, the film of cathode materials, and the film of solid electrolyte materials to increase the density of the at least one of the film of anode materials, the film of cathode materials, and the film of solid electrolyte materials, by thermal consolidation and mechanical consolidation, 
 wherein:
 - the respective thicknesses of the deposited film of anode materials, the deposited film of cathode materials, and the deposited solid electrolyte materials are less than 5 μm, and 
 - the consolidation is further performed under a vacuum or an inert atmosphere, the at least one of the film of anode materials, the film of cathode materials, and the film of solid electrolyte materials.